Eran Greenberg

Polymorphism in a high-entropy alloy

Polymorphism, which describes the occurrence of different lattice structures in a crystalline material, is a critical phenomenon in materials science and condensed matter physics. Recently, configuration disorder was compositionally engineered into single lattices, leading to the discovery of high-entropy alloys and high-entropy oxides. For these novel entropy-stabilized forms of crystalline matter with extremely high structural stability, is polymorphism still possible? Here by employing in situ high-pressure synchrotron radiation X-ray diffraction, we reveal a polymorphic transition from face-centred-cubic (fcc) structure to hexagonal-close-packing (hcp) structure in the prototype CoCrFeMnNi high-entropy alloy. The transition is irreversible, and our in situ high-temperature synchrotron radiation X-ray diffraction experiments at different pressures of the retained hcp high-entropy alloy reveal that the fcc phase is a stable polymorph at high temperatures, while the hcp structure is more thermodynamically favourable at lower temperatures. As pressure is increased, the critical temperature for the hcp-to-fcc transformation also rises.

Stable high-pressure phases in the H-S system determined by chemically reacting hydrogen and sulfur

Synchrotron X-ray diffraction and Raman spectroscopy have been used to study chemical reactions of molecular hydrogen (H2) with sulfur (S) at high pressures. We find theoretically predicted Cccm and Im-3m H3S to be the reaction products at 50 and 140 GPa, respectively. Im-3m H3S is a stable crystalline phase above 140 GPa and it transforms to R3m H3S on pressure release below 140 GPa. The latter phase is (meta)stable down to at least 70 GPa where it transforms to Cccm H3S upon annealing (T<1300 K) to overcome the kinetic hindrance. Cccm H3S has an extended structure with symmetric hydrogen bonds at 50 GPa and upon decompression it experiences a transformation to a molecular mixed H2S-H2 structure below 40 GPa without any apparent change in the crystal symmetry.

Mott transition in CaFe 2 O 4 at around 50 GPa

ossbauer spectroscopy (MS), Raman spectroscopy, and electrical resistance measurements. These studies have shown the onset of the Mott transition (MT) at a pressure of around 50 GPa, leading to the collapse of Fe 3+ magnetic moments and to the insulator-metal (IM) transition. The observed onset of the MT corroborates with the recently reported isostructural transition accompanied by a 12% decrease in the Fe polyhedral volume. An analysis of the alterations of the electrical transport, magnetic, and structural properties with pressure increase and at the transition range suggests that the coinciding IM transition, magnetic moment, and volume collapse at around 50 GPa are caused by the closure of the Hubbard gap driven by the high-spin to low-spin (HS-LS) transition. At that, since MS did not reveal any evidence of a preceding LS state, it could be inferred that the HS-LS transition immediately leads to an IM transition and complete collapse of magnetism.

Pressure-induced structural phase transition of the iron end-member of ringwoodite (γ-Fe2SiO4) investigated by X-ray diffraction and Mössbauer spectroscopy

Abstract We have carried out X-ray diffraction and Mössbauer spectroscopy measurements on the spinel phase g-Fe2SiO4 (ringwoodite) at ambient temperature and pressures up to 66 GPa using diamond anvil cells. At pressures above 30 GPa, a previously unknown structural phase transition to a rhombohedrally distorted spinel phase has been observed (space group R3̄mR). Mössbauer spectroscopy measurements reveal two different Fe2+ sites at high pressure with an abundance ratio of 3:1, in agreement with the two crystallographic sites occupied by the iron in this distorted spinel structure. The unit-cell volume of the low-pressure spinel phase as a function of pressure results in a bulk modulus of K0 = 197(3) GPa using the second-order Birch-Murnaghan equation of state, and K0 = 201(8) GPa and K′ = 3.7(7) when using a third-order equation of state. The pressure evolution of the unit-cell volume and the Mössbauer hyperfine parameters are in good agreement with previous studies, which were limited to a lower pressure range.

Raman spectroscopy and X-ray diffraction of sp3-CaCO3 at lower mantle pressures

The exceptional ability of carbon to form sp2 and sp3 bonding states leads to a great structural and chemical diversity of carbon-bearing phases at non-ambient conditions. Here we use laser-heated diamond anvil cells combined with synchrotron x-ray diffraction, Raman spectroscopy, and first-principles calculations to explore phase transitions in CaCO3 at P > 40 GPa. We find that post-aragonite CaCO3 transforms to the previously predicted P21/c-CaCO3 with sp3-hybridized carbon at 105 GPa (~30 GPa higher than the theoretically predicted crossover pressure). The lowest enthalpy transition path to P21/c-CaCO3 includes reoccurring sp2- and sp3-CaCO3 intermediate phases and transition states, as reveled by our variable-cell nudged elastic band simulation. Raman spectra of P21/c-CaCO3 show an intense band at 1025 cm-1, which we assign to the symmetric C-O stretching vibration based on empirical and first principles calculations. This Raman band has a frequency that is ~20 % lower than the symmetric C-O stretching in sp2-CaCO3, due to the C-O bond length increase across the sp2-sp3 transition, and can be used as a fingerprint of tetrahedrally-coordinated carbon in other carbonates.

Pressure-induced structural transition in chalcopyrite ZnSiP2

The pressure-dependent phase behavior of semiconducting chalcopyrite ZnSiP2 was studied up to 30 GPa using in situ X-ray diffraction and Raman spectroscopy in a diamond-anvil cell. A structural phase transition to the rock salt type structure was observed between 27 and 30 GPa, which is accompanied by soft phonon mode behavior and simultaneous loss of Raman signal and optical transmission through the sample. The high-pressure rock salt type phase possesses cationic disorder as evident from broad features in the X-ray diffraction patterns. The behavior of the low-frequency Raman modes during compression establishes a two-stage, order-disorder phase transition mechanism. The phase transition is partially reversible, and the parent chalcopyrite structure coexists with an amorphous phase upon slow decompression to ambient conditions.

Superconductivity in multiple phases of compressed GeSb2Te4

Here we report the discovery of superconductivity in multiple phases of the compressed GeSb2Te4 (GST) phase change memory alloy, which has attracted considerable attention for the last decade due to its unusual physical properties with many potential applications. Superconductivity is observed through electrical transport measurements, both for the amorphous (a-GST) and for the crystalline (c-GST) phases. The superconducting critical temperature, TC, continuously increases with the applied pressure reaching a maximum Tc =6K at P=20 GPa for a-GST, whereas the critical temperature of the cubic phase reaches a maximum Tc =8 K at 30 GPa. This new material system, exhibiting a superconductor-insulator quantum phase transition (SIT) has an advantage over disordered metals since it has a continuous control of the crystal structure and the electronic properties using pressure as an external stimulus, which was lacking in SIT studies until today.

Structural phase transitions in SrTiO3 nanoparticles

Understanding the structural phase diagram of nano scale SrTiO3 has important implications on the basic physics and applications of the general class of transition metal oxide perovskites. Pressure dependent structural measurements on monodispersed nanoscale SrTiO3 samples with average diameters of 10 to ~80 nm were conducted. A robust pressure independent polar structure was detected in the 10 nm sample for pressures of up to 13 GPa while a size dependent cubic to tetragonal transition occurs (at P = Pc) for larger particle sizes. The results suggest that the growth of ~10 nm STO particles on substrates with large lattice mismatch will not alter the polar state of the system for a large range of strain values, possibly enabling device use.

Global geolocation of intense lightning strokes associated with TLEs based on ELF measurements from single-station

A new, improved algorithm has been developed to geolocate intense lightning strokes around the globe. In the ELF (extremely low frequency) range, radio waves from lightning propagate in the Earth-ionosphere cavity and quasi-TEM is effectively the only radiated mode. The spectra depend on the distance between the source (lightning) and the observer. Based on theoretically predicted spectra, a numerical data base was established to compare with our experimental data. The algorithm allowed us to determine SOD (source-observer distance) with high resolution (50 km) while the source bearing was determined through a Lissajous figure for the magnetic field and Poynting vector components using a least-squares fitting method. The algorithm and ELF electromagnetic data from other groups allowed us to geolocate lightning strokes associated with TLEs (transient luminous events) which were observed from the Columbia space shuttle during MEIDEX with the first Israeli astronaut, Ilan Ramon, aboard.

Uranium polyhydrides at moderate pressures: Prediction, synthesis, and expected superconductivity

Formation of uranium polyhydrides UH5–9 is predicted using the evolutionary algorithm USPEX and proved by high-pressure synthesis. Hydrogen-rich hydrides attract great attention due to recent theoretical (1) and then experimental discovery of record high-temperature superconductivity in H3S [Tc = 203 K at 155 GPa (2)]. Here we search for stable uranium hydrides at pressures up to 500 GPa using ab initio evolutionary crystal structure prediction. Chemistry of the U-H system turned out to be extremely rich, with 14 new compounds, including hydrogen-rich UH5, UH6, U2H13, UH7, UH8, U2H17, and UH9. Their crystal structures are based on either common face-centered cubic or hexagonal close-packed uranium sublattice and unusual H8 cubic clusters. Our high-pressure experiments at 1 to 103 GPa confirm the predicted UH7, UH8, and three different phases of UH5, raising confidence about predictions of the other phases. Many of the newly predicted phases are expected to be high-temperature superconductors. The highest-Tc superconductor is UH7, predicted to be thermodynamically stable at pressures above 22 GPa (with Tc = 44 to 54 K), and this phase remains dynamically stable upon decompression to zero pressure (where it has Tc = 57 to 66 K).